JP2017521463A - Sunscreen formulations optimized for vitamin D formation - Google Patents

Abstract

The present invention includes (a) triazine derivatives; (b) cinnamic acid derivatives; (c) bis-resorcinyl triazines; (f) benzimidazole derivatives; (i5) 4-methylbenzylidene camphors; (h) benzoylpiperazine derivatives; (j) benzoxazole derivative; (k) diarylbutadiene derivative; (l) phenylbenzotriazole derivative; (n) benzylidene malonate; (o3) salicylic acid TEA; (r) imidazoline derivative; (u) selected from metal oxides (V) naphthalate; and (w) at least one UV filter (A) selected from merocyanine derivatives; and optionally (d) an aminobenzophenone derivative; (e) dibenzoylmethane (G) β, β-diphenyl acrylate derivatives; (i5) different camphor derivatives; (o3) different salicylate derivatives; (p) anthranilate derivatives; and (s) benzalmalonate derivatives A sunscreen formulation comprising at least one of the selected UV filters (B), in order to increase the transmission of UV radiation in human skin for the production of cholecalciferol (previtamin D3), And at the same time, a method for protecting human skin against UV radiation when exposed to sunlight, for previtamin D3 formation for use in a method comprising applying said sunscreen formulation to the skin A sunscreen formulation wherein the ratio R of effective irradiance Epvd to eruption and effective irradiance Eer for erythema formation in the skin is at least 1.8. [Selection figure] None

Description

The present invention increases the transmittance of UV radiation for the production of cholecalciferol (previtamin D ₃ ) in human skin, while at the same time human skin against said UV radiation when exposed to sunlight. Relates to a method for protecting.

  It is well known that chronic exposure to sunlight can have damaging effects on human skin. Depending on the wavelength, UV radiation causes different types of skin damage. UV-B radiation (about 290 to about 320 nm) is a cause of sunburn and can cause skin cancer. UV-A radiation (about 320 to about 400 nm) causes skin tanning while also contributing to the induction of sunburn and skin cancer.

  Nowadays, it is well recognized that proper sun protection should include broadband protection, that is, sunscreen should protect both UVA and UVB radiation. Since 2006, the European recommendation requires minimal UVA protection with respect to the level of UVB protection, which means that UVA-PF (UVA protection factor) is at least 1/3 of SPF (sun protection factor).

Apart from the damaging effects of the known UV radiation, a certain amount of UVB radiation is needed for the formation of vitamin D ₃ and its precursor in the skin.

In order to prevent sunburn, reducing the effective erythema dose (= E _r ) using sunscreen also reduces the effective dose (= E _pvD ) that causes vitamin D ₃ formation. Thus, the sunscreen, might production of vitamin D ₃ in the skin is reduced, or may even be prevented. This is not surprising, since, tanning radiation is responsible for causing (erythema) and skin damage is in the same range as the radiation range which is also the cause of skin vitamin D ₃ synthesis. It was shown that topical application of a sun protection factor of 8 sunscreen prevented any increase in vitamin D ₃ blood levels after systemic exposure to simulated sunlight that caused a mild sunburn. Thus, using sunscreen reduces the body's own production of vitamin D ₃ and the use of chronic sunscreen can result in undesirable low vitamin D ₃ blood levels.

The problem underlying the present invention is to find a sunscreen to prevent vitamin D ₃ formation inhibition between the exposure to sunlight.

  Surprisingly, it has been found that sunscreens comprising at least one specific UV filter meet these requirements.

Therefore, the present invention
(a) a triazine derivative;
(b) cinnamic acid derivatives;
(c) bis-resorcinyl triazine;
(f) benzimidazole derivatives;
(i ₅₎ 4-methyl benzylidene camphor;
(h) a benzoylpiperazine derivative;
(j) benzoxazole derivatives;
(k) a diarylbutadiene derivative;
(l) phenylbenzotriazole derivatives;
(n) benzylidene malonate;
(o ₃ ) salicylic acid TEA;
(r) an imidazoline derivative;
(u) an inorganic UV filter selected from metal oxides;
(v) naphthalate; and
(w) comprising at least one UV filter (A) selected from merocyanine derivatives; and optionally
(d) an aminobenzophenone derivative;
(e) a dibenzoylmethane derivative;
(g) β, β-diphenyl acrylate derivative;
(i) camphor derivatives different from (i ₅ );
a salicylate derivative different from (o) (o ₃ );
(p) an anthranilate derivative; and
(s) a sunscreen formulation comprising at least one UV filter (B) selected from benzalmalonate derivatives,
-In order to increase the transmittance of UV radiation in human skin for the production of vitamin D ₃ and at the same time in a way to protect human skin against UV radiation when exposed to sunlight For use in a method comprising applying the sunscreen formulation to the skin,
The invention relates to a sunscreen preparation, wherein the ratio R of the effective dose E _pvd for vitamin D ₃ formation to the effective dose E _er for erythema formation in the skin is at least 1.8.

Figure 1: Ratio of effective dose for vitamin D ₃ formation to erythema formation R = E _pvD / E _er under natural sunlight conditions. Figure 3: Simulated UV transmission of four SPF6 sunscreens (compositions in Table 1) for strong UVA (A1.3) and vitamin D ₃ (A1.4) with optimized protective properties Spectrum. Figure 4: Simulated UV transmission of four SPF15 sunscreens (compositions in Table 2) for strong UVA (A2.3) and vitamin D ₃ (A2.4) with optimized protective properties Spectrum. Figure 5: Simulated UV transmission spectra of four SPF30 sunscreens (compositions in Table 3) for strong UVA (A3.3) and vitamin D (A3.4) with optimized protective properties .

Effective dose Effective dose E _er is the following formula:
(EI _er ): Effective dose for erythema formation E _er E _er = ∫S (λ) s _er (λ) dλ
(EI _pvD ): Effective dose for vitamin D ₃ formation E _pvD E _pvD = ∫S (λ) s _VD (λ) dλ
According to the above, at any wavelength in the spectral region, the irradiation dose of the light source (= standard sunlight exposure dose S (λ)), the action spectrum s _er (λ) for erythema formation and s _pvD (λ) for vitamin D ₃ production, respectively Can be calculated respectively.

である。 Under natural sunlight conditions, the ratio of effective dose to vitamin D ₃ formation and effective dose to erythema formation R = E _pvD / E _er is approximately

It is.

  This can be illustrated by FIG.

  The classification of UV filters as defined in claim 1 includes various types of UV filters: UB-B filters (290-320 nm), UV-AII filters (320-340 nm), and broad spectrum and UV-AI filters. (340-400 nm) is included.

  Listed below are typical examples of general UV filter classifications.

に相当する5,6,5',6'-テトラフェニル-3,3'-(1,4-フェニレン)ビス(1,2,4-トリアジン);
(a₆)式

の安息香酸,4,4'-[[6-[[3-[1,3,3,3-テトラメチル-1-[(トリメチルシリル)オキシ]-1-ジシロキサニル]プロピル]-アミノ]-1,3,5-トリアジン-2,4-ジイル]ジイミノ]ビス-,ジブチルエステル
から選択される。 Suitable triazine derivatives (a) are:
(a ₁ ) ethylhexyltriazone;
(a ₂ ) tris-biphenyltriazine;
(a ₃ ) diethylhexylbutamide triazone;
(a ₄ ) phenylenebis-diphenyltriazine;
(a ₅ ) formula

5,6,5 ', 6'-tetraphenyl-3,3'-(1,4-phenylene) bis (1,2,4-triazine) corresponding to
(a ₆ ) formula

Benzoic acid, 4,4 '-[[6-[[3- [1,3,3,3-tetramethyl-1-[(trimethylsilyl) oxy] -1-disiloxanyl] propyl] -amino] -1, 3,5-triazine-2,4-diyl] diimino] bis-, dibutyl ester.

の2-プロぺン酸,3-(4-エトキシフェニル)-,2-メチルフェニルエステル;
(b₈)式

の2-プロペン酸,3-(4-メトキシフェニル)-,2-メチルフェニルエステル;
(b₉)式

のプロパン二酸,2-[(4-メトキシフェニル)メチレン]-,1,3-ビス(2-メチルブチル)エステル
(b₁₀)式

のプロパン二酸,2-[(4-メトキシフェニル)メチレン]-,1,3-ビス(2-エチルヘキシル)エステル
から選択される。 Suitable cinnamic acid derivatives (b) are:
(b ₁ ) ethylhexyl methoxycinnamate;
(b ₂ ) isopropyl methoxycinnamate;
(b ₃ ) isoamyl methoxycinnamate;
(b ₄ ) methyl diisopropylcinnamate;
(b ₅ ) cinnoxate;
(b ₆ ) glyceryl ethylhexanoate;
(b ₇ ) formula

2-propenoic acid, 3- (4-ethoxyphenyl)-, 2-methylphenyl ester;
(b ₈ ) formula

2-propenoic acid, 3- (4-methoxyphenyl)-, 2-methylphenyl ester;
(b ₉ ) formula

Propanedioic acid, 2-[(4-methoxyphenyl) methylene]-, 1,3-bis (2-methylbutyl) ester
(b ₁₀ ) formula

Of propanedioic acid, 2-[(4-methoxyphenyl) methylene]-, 1,3-bis (2-ethylhexyl) ester.

Suitable bis-resorcinyl triazines (c) are
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine; and
(c ₂ ) selected from aqueous dispersions of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate.

Suitable aminobenzophenone derivatives (d) are:
(d ₁ ) Selected from diethylaminohydroxybenzoyl hexyl benzoate.

Suitable dibenzoylmethane derivatives (e) are
(e ₁₎ butylmethoxydibenzoylmethane; and
(e ₂ ) Selected from isopropyldibenzoylmethane.

Suitable benzimidazole derivatives (f) are
(f ₁ ) phenylbenzimidazole sulfonic acid; and
(f ₂ ) selected from disodium phenyldibenzimidazole tetrasulfonate.

Suitable β, β-diphenyl acrylate derivatives (g) are:
(g ₁ ) octocrylene; and
(g ₂ ) selected from ethocrylene.

Suitable benzoylpiperazine derivatives (h) are:
(h ₁ ) 1,4- (2- (4-Diethylamino-2-hydroxybenzoyl) benzoyl) piperazine is selected.

Suitable camphor derivatives (i) are:
(i ₁ ) terephthalylidene dicamphor sulfonic acid;
(i ₂ ) benzylidene camphor sulfonic acid;
(i ₃ ) camphor benzalkonium methosulfate;
(i ₄ ) 3-benzylidene camphor;
(i ₅ ) methylbenzylidene camphor; and
(i ₆ ) selected from polyacrylamide methylbenzylidene camphor.

Suitable benzoxazole derivatives (j) are
(j ₁ ) selected from ethylhexyl bis-isopentylbenzoxazolylphenyl melamine.

Suitable diaryl butadiene derivatives (k) are:
(k ₁ ) selected from 1,1-dicarboxy (2,2′-dimethyl-propyl) -4,4-diphenylbutadiene.

のフェノール,2-(2H-ベンゾトリアゾール-2-イル)-6-[[(2-エチルヘキシル)オキシ]メチル]-4-メチル-
(l₄)ベンゾトリアゾリルドデシルp-クレゾール;
(l₅)US20110195036、WO2011097555に記載された高分子ベンゾトリアゾールタイプのUVフィルター;例えば、ダイマージオール(C₃₆H₇₂O)、ジトリメチロールプロパン、アジピン酸ジメチル、アジピン酸メチル、及びメチル3-(2H-ベンゾトリアゾール-2-イル)-5-(1,1-ジメチルエチル)-4-ヒドロキシベンゼンプロパノエートから調製されたポリマー;並びに
(l₆)式

に相当する2-(2H-ベンゾトリアゾール-2-イル)-6-(2-エチルヘキシルオキシメチル)-4-メチル-フェノール
から選択される。 Suitable phenylbenzotriazole derivatives (l) are:
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(l ₃ ) formula

Of phenol, 2- (2H-benzotriazol-2-yl) -6-[[(2-ethylhexyl) oxy] methyl] -4-methyl-
(l ₄ ) benzotriazolyldodecyl p-cresol;
(l ₅ ) Polymeric benzotriazole type UV filters described in US20110195036, WO2011097555; for example, dimer diol (C ₃₆ H ₇₂ O), ditrimethylolpropane, dimethyl adipate, methyl adipate, and methyl 3- (2H -Benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxybenzenepropanoate; and
(l ₆ ) formula

2- (2H-benzotriazol-2-yl) -6- (2-ethylhexyloxymethyl) -4-methyl-phenol corresponding to

(式中、R₁は、メチル;エチル;プロピル;又はn-ブチルであり;
次いで、R₁がメチルである場合、
Rはtertブチル;

;式

の基;又は式

の基であり;
R₂及びR₃は、互いに独立して水素;又はメチルであり;
R₄はメチル;エチル;又はn-プロピルであり;
R₅及びR₆は、互いに独立して水素;又はC₁〜C₃アルキルであり;
次いで、R₁がエチル;プロピル;又はn-ブチルである場合、
Rはイソプロピルである)のベンジリデンマロネート
から選択される。 Suitable malonic acid derivatives (n) are:
(n ₁ ) formula

Wherein R ₁ is methyl; ethyl; propyl; or n-butyl;
Then when R ₁ is methyl,
R is tertbutyl;

;formula

A group of

A radical of;
R ₂ and R ₃ are independently of each other hydrogen; or methyl;
R ₄ is methyl; ethyl; or n-propyl;
R ₅ and R ₆ are independently of each other hydrogen; or C ₁ -C ₃ alkyl;
Then when R ₁ is ethyl; propyl; or n-butyl,
R is isopropyl) benzylidene malonate.

の基であり;及び
R₁はメチルである。 Preferably, in formula (BM):
R is the formula

A radical of; and
R ₁ is methyl.

の化合物が最も好ましい。 formula

The most preferred compound is

  Examples of compounds of formula (BM) are listed in Table 1 below.

に相当するジエチルヘキシルシリンジリデンマロネート
を指す。 More suitable malonate (n) is
(n ₂ ) formula

Refers to diethylhexyl syringe redene malonate.

Suitable salicylate derivatives are
(o ₁ ) ethylhexyl salicylate;
(o ₂ ) dipropylene glycol salicylate;
(o ₃ ) salicylic acid TEA; and
(o ₄ ) selected from homosalate.

Suitable anthranilate derivatives (p) are
(p ₁ ) refers to menthyl anthranilate.

Suitable imidazoline derivatives (r) are:
(r ₁ ) ethylhexyldimethoxybenzylidene; and
(r ₂ ) selected from dioxoimidazoline propionate.

Suitable benzalmalonate derivatives are:
(s ₁ ) Polysilicone-15
Selected from.

Suitable inorganic UV filters (u)
(u ₁ ) zinc oxide;
(u ₂ ) Fe ₂ O ₃ ; and
(u ₃ ) selected from titanium dioxide.

Suitable naphthalate (v) is
(v ₁ ) selected from diethylhexyl 2,6-naphthalate.

  Preferably, the sunscreen formulation according to the invention has an SPF of at least 2.

  More preferably, the sunscreen formulation according to the invention has an SPF of at least 6.

  Sunscreen formulations according to the invention comprise one or more than one UV filter.

  For example, a sunscreen formulation according to the invention may comprise 1, 2, 3, 4, 5 or 6 UV filters selected from the classification of UV filters as defined in claim 1.

Preferably, the sunscreen formulation according to the present invention comprises
(a ₁ ) ethylhexyltriazone;
(a ₂ ) tris-biphenyltriazine;
(a ₃ ) diethylhexylbutamide triazone;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(g ₁ ) octocrylene;
(h ₁ ) 1,4- (2- (4-diethylamino-2-hydroxybenzoyl) benzoyl) piperazine;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(l ₆ ) 2- (2H-benzotriazol-2-yl) -6- (2-ethylhexyloxymethyl) -4-methyl-phenol;
(i ₁ ) terephthalylidene dicamphor sulfonic acid;
(n ₁ ) a compound of formula (BM9);
(o ₁ ) ethylhexyl salicylate;
(o ₄ ) homosalate;
(p ₁ ) menthyl anthranilate;
(s ₁ ) Polysilicone-15;
(u ₁ ) zinc oxide; and
(u ₃ ) including a UV filter selected from titanium dioxide.

More preferably, the sunscreen formulation according to the present invention comprises
(a ₁ ) ethylhexyltriazone;
(b ₁ ) ethylhexyl methoxycinnamate;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid;
(g ₁ ) octocrylene; and
(u ₃ ) including a UV filter selected from titanium dioxide.

  Preferably, the sunscreen formulation has an SPF of at least 6.

Even more preferably, the sunscreen formulation according to the present invention comprises
(b ₁ ) ethylhexyl methoxycinnamate;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid; and
(g ₁ ) octocrylene;
Includes a UV filter selected from.

  Preferably, the sunscreen formulation has an SPF of at least 6.

Furthermore, the sunscreen formulation according to the present invention is:
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol; and
It is preferred to include a UV filter selected from (e ₁ ) butylmethoxydibenzoylmethane.

  Preferably, the sunscreen formulation has an SPF of at least 6.

Preferably, the sunscreen formulation according to the present invention comprises
(a) 0.1-40% bw triazine derivative;
(b) 0.1-30% bw cinnamic acid derivative;
(c) 0.1-10% bw bis-resorcinyl triazine;
(f) 0.1-10% bw benzimidazole derivative;
(i ₅ ) 0.1-10% bw 4-methylbenzylidene camphor;
(h) 0.1-10% bw benzoylpiperazine derivative;
(j) 0.1-10% bw benzoxazole derivative;
(k) 0.1-20% bw diarylbutadiene derivative;
(l) 0.1-30% bw phenylbenzotriazole derivative;
(n) 0.1-20% bw benzylidene malonate;
(o ₃ ) 0.1-15% bw salicylic acid TEA;
(r) 0.1-10% bw imidazoline derivative;
(u) Inorganic UV filter selected from 0.1-50% bw metal oxide;
(v) 0.1-20% bw naphthalate; and
(w) 0.1-20% bw merocyanine derivative;
A UV filter concentrate selected from, and in some cases,
(d) 0.1-20% bw aminobenzophenone derivative;
(e) 0.1-5% bw dibenzoylmethane derivative;
(g) 0.1-1% bw of β, β-diphenylacrylate derivative;
(i) 0.1-10% bw camphor derivative different from (i ₅ );
(o) 0.1-35% bw salicylate derivative different from (o ₃ );
(p) 0.1-10% bw anthranilate derivative; and
(s) comprises at least one UV filter (B) selected from 0.1 to 10% bw benzalmalonate derivatives.

More preferably, the sunscreen formulation according to the present invention comprises
(a ₁ ) 1-3% bw ethylhexyl triazone;
(b ₁ ) 1-3.5% bw ethylhexyl methoxycinnamate;
(c ₁ ) 0.6-10% bw bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) 0.8-10% bw diethylaminohydroxybenzoyl hexyl benzoate;
(e ₁ ) 2-3% bw butylmethoxydibenzoylmethane;
(f ₁ ) 2-3% bw phenylbenzimidazole sulfonic acid;
(g ₁ ) 2.0-2.5% bw octocrylene;
(l ₁ ) 2 to 7.5% bw methylenebis-benzotriazolyltetramethylbutylphenol; and
containing (u ₃₎ UV filters concentrate selected from titanium dioxide 3.0-3.5% bw.

The sunscreen preparation according to the present invention comprises:
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol; and
(e ₁ ) butylmethoxydibenzoylmethane; most preferably
(d ₁ ) 9.0-11.0% bw diethylaminohydroxybenzoyl hexyl benzoate;
(l ₁ ) 2.5-3.5% bw methylenebis-benzotriazolyltetramethylbutylphenol; and
(e ₁ ) SPF of> 15 is achieved by using a UV filter combination of 2.5-3.5% bw butylmethoxydibenzoylmethane.

The sunscreen preparation according to the present invention comprises:
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol; and
(e ₁ ) butylmethoxydibenzoylmethane; most preferably
(c ₁ ) 1.5-2.5% bw bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) 9.5 to 10.5% bw diethylaminohydroxybenzoyl hexyl benzoate;
(l ₁ ) 7-8% bw methylenebis-benzotriazolyltetramethylbutylphenol; and
(e ₁ ) SPF of> 30 is achieved by using a UV filter combination of 2.5-3.5% bw butylmethoxydibenzoylmethane.

Preferably, the UV filter is a broadband (340-400 nm spectrum) UV filter
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(u ₁ ) zinc oxide; and, in some cases,
(e ₁ ) butylmethoxydibenzoylmethane;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(i ₁ ) terephthalylidene dicamphor sulfonic acid; and
(p ₁ ) A sunscreen preparation according to the invention selected from menthyl anthranilate is used.

Furthermore, the present invention provides
(a) Triazine derivative
(b) cinnamic acid derivatives;
(c) bis-resorcinyl triazine;
(f) benzimidazole derivatives;
(h) a benzoylpiperazine derivative;
(i ₅₎ 4-methyl benzylidene camphor;
(l) phenylbenzotriazole derivatives;
(n) benzylidene malonate;
(o ₃ ) salicylic acid TEA;
(r) an imidazoline derivative;
(u) an inorganic UV filter selected from metal oxides;
(v) naphthalate; and
(w) including a UV filter selected from merocyanine derivatives;
Refers to a sunscreen formulation containing only one of the selected UV filters.

Preferably, the UV filter is a broadband (340-400 nm spectrum) UV filter
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(i ₁ ) terephthalylidene dicamphor sulfonic acid; and
(u ₁ ) zinc oxide;
Selected from
Sunscreen formulations are used, containing only one of the selected UV filters.

further,
(a ₂ ) tris-biphenyltriazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(h ₁ ) 1,4- (2- (4-diethylamino-2-hydroxybenzoyl) benzoyl) piperazine;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(u ₁ ) zinc oxide; and
(u ₃ ) A sunscreen formulation comprising a particulate UV filter selected from titanium dioxide is preferred.

further,
(a ₁ ) ethylhexyltriazone;
(a ₃ ) diethylhexylbutamide triazone;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(g ₁ ) octocrylene;
(h ₁ ) 1,4- (2- (4-diethylamino-2-hydroxybenzoyl) benzoyl) piperazine;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(l ₆ ) 2- (2H-benzotriazol-2-yl) -6- (2-ethylhexyloxymethyl) -4-methyl-phenol;
(i ₁ ) terephthalylidene dicamphor sulfonic acid;
(n ₁ ) a compound of formula (BM9);
(o ₁ ) ethylhexyl salicylate;
(o ₄ ) homosalate;
(p ₁ ) menthyl anthranilate; and
(s ₁ ) Polysilicone-15
A sunscreen formulation comprising a non-particulate UV filter selected from is preferred.

The preferred ratio of the effective dose E _pvd for vitamin D ₃ formation and the effective dose E _er for erythema formation in the skin of the sunscreen preparation according to the invention is at least 1.8, preferably at least 1.85, more preferably at least 1.90, Even more preferably> 1.95, most preferably at least 2.0, most preferably at least 2.1.

Furthermore, according to the invention, the ratio of the effective dose E _pvd for vitamin D ₃ formation to the effective dose E _er for erythema formation in the skin is at least 1.8 and contains the UV filter combination CSF1-CSF32 of Table 1 Sunscreen formulations are preferred.

According to the present invention, the sun protection factor (abbreviated as SPF) proposed by the European Commission recommendation, including but not limited to:> SPF 60, including SPF 6, 15, 30, 50 and 50+ (> 60) Sunscreen compositions with optimized permeability for improved vitamin D ₃ production can be provided with a wide range of SPFs up to. According to EC recommendation, SPF6 belongs to the category of “low protection”, SPF15 is “medium protection”, SPF30 and 50 are “high protection”, SPF50 + (Requires a minimum of SPF 60) belongs to "very high protection".

  Regarding broadband protection, the EC recommendation states that the UVA-PF / SPF ratio should be at least 1/3 and the critical wavelength (CW) should be at least 370 nm. For low UVA protection, the UVA-PF / SPF ratio is significantly lower, and for advanced UVA protection, the UVA-PF / SPF ratio is much higher than 1/3.

Sunscreen inevitably reduces both E _er and E _pvd in the skin. The ratio R = E _pvd / E _er is optimized by selecting an appropriate UV filter combination. As the ratio R is high, sunscreen performance for vitamin D ₃ production for a given protection to E _er it is improved.

The sunscreen preparations according to the invention are particularly useful for the protection of human and animal skin and hair against the action of organic substances sensitive to ultraviolet light, in particular UV radiation, while at the same time producing vitamin D _{3 in} human skin. Particularly useful for increasing the transmittance of UV radiation. Such UV filter combinations are therefore suitable as photoprotective agents in cosmetic and pharmaceutical formulations.

  A sunscreen formulation according to the invention is a combination of UV filters as defined in claim 1 of 1 to 50% by weight, preferably 1 to 20% by weight, preferably 3 to 15% by weight, based on the total weight of the formulation, And a cosmetically acceptable adjuvant.

Sunscreen formulations according to the present invention are prepared by physically mixing the UV filter as defined in claim 1 with an adjuvant using conventional methods, for example by simply stirring the individual components together. It can be prepared by taking advantage of the dissolution properties of already known cosmetic UV absorbers such as ethylhexyl methoxycinnamate (UV filter component (b ₁ )). The UV filter as defined in claim 1 can be used in sunscreen formulations, for example without further processing.

Some of the UV filters used in the sunscreen formulations of the present invention, such as (l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol, (a ₂ ) tris-biphenyltriazine or (h ₁ ) 1,4- (2 -(4-Diethylamino-2-hydroxybenzoyl) benzoyl) piperazine can be used in their micronized state (nanoscale organic filters, particulate organic filters, UV absorber pigments).

Any known method suitable for the preparation of microparticles, for example a wet mill using hard grinding media, such as zirconium silicate balls in a ball mill, and a protective surfactant or protective polymer in water or in a suitable organic solvent (Method of making the viscosity of the dispersion that can be pumped low), wet kneading using a continuous or non-continuous (batch type) kneader (method of making the viscosity of the paste that cannot be pumped), appropriate Spray drying from various solvents, expansion of supercritical fluids (e.g. CO ₂ ) by the RESS method (supercritical solution rapid expansion method), or precipitation from suitable solvents containing supercritical fluids can be used to prepare micronized UV filters. Can be used.

  Suitable mill equipment for the preparation of the finely divided organic UV filter is, for example, a jet mill, a ball mill, a vibration mill or a hammer mill, preferably a high speed mixing mill or a ball mill. The grinding is preferably carried out using a grinding aid.

  The micronized UV filter thus obtained usually has an average particle size of 0.02 to 2 micrometers, preferably 0.05 to 1.5 micrometers, and more particularly 0.1 to 1.0 micrometers.

  The micronized UV filter used in the present invention is preferably present as an aqueous dispersion. The grinding of the slightly soluble organic compounds used in the present invention is preferably carried out using grinding aids. The dispersant is used as a low molecular weight grinding aid for all of the above-described methods of atomization. Preferred useful aqueous dispersion grinding aids are anionic surfactants with HLB values greater than 8, more preferably greater than 10. Any conventionally useful anionic, nonionic or amphoteric surfactant can be used as a dispersant (component (b)). Such surfactant systems include, for example, carboxylic acids and their salts: organic soaps such as alkaline soaps of sodium, potassium and ammonia, metal soaps of calcium or magnesium, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid. Base soap. Alkyl phosphoric acid or phosphoric acid ester, acidic phosphoric acid ester, diethanolamine phosphate, potassium cetyl phosphate. Ethoxylated carboxylic acid or polyethylene glycol ester, PEG-n acrylate. Aliphatic alcohol polyglycol ethers such as laureth-n, milles-n, cetealess-n, steareth-n, oleth-n. Fatty acid polyglycol ethers such as PEG-n stearate, PEG-n oleate, PEG-n palm fatty acid. Monoglycerides and polyol esters. C12-C22 fatty acid mono- and diesters of addition products of 1-100 moles of ethylene oxide and polyols. Fatty acids and polyglycerol esters such as glycerol monostearate, diisostearoyl polyglyceryl-3 diisostearate, polyglyceryl-3 diisostearate, triglyceryl diisostearate, polyglyceryl-2 sesquiisostearate or polyglyceryl dimerate. Mixtures of compounds from a plurality of these substance classes are also suitable. Fatty acid polyglycol esters such as diethylene glycol monostearate, fatty acids and polyethylene glycol esters, sucrose esters such as fatty acids and sucrose esters, sucrose esters such as glycerol and sucrose glycerides. Sorbitol and sorbitan, sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and ethylene oxide addition products. Polysorbate-n series, sorbitan esters such as sesquiisostearic acid, sorbitan, PEG- (6) sorbitan isostearate, PEG- (10) -sorbitan laurate, PEG-17-diolate sorbitan. Ethoxylated analogues using glucose derivatives, C8-C22 alkyl mono- and oligoglycosides and preferred glucose as the sugar component. O / W emulsifiers such as methyl sesquistearate, sorbitan stearate / coconut fatty acid sucrose, methyl glucose sesquistearate, cetearyl alcohol / cetearyl glucoside. W / O emulsifiers such as methyl glucose dioleate / methyl glucose isostearate. Sulfate and sulfonated derivatives, dialkyl sulfosuccinate, dioctyl succinate, alkyl lauryl sulfonate, linear sulfonated paraffin, sulfonated tetraproprine sulfonate, sodium lauryl sulfate, ammonium lauryl sulfate and ethanolamine, lauryl ether sulfate, Sodium laureth sulfate or sodium milles sulfate, sulfosuccinate, acetyl isothionate, sulfate alkanolamide, taurine, methyl taurine, imidazole sulfate. Zwitterionic or amphoteric surfactants having at least one quaternary ammonium group and at least one carboxylate and / or sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are betaines such as N-alkyl-N, N-dimethylammonium glycinates, each having 8 to 18 carbon atoms in the alkyl or acyl group, coconut oil alkyldimethylammonium glycine. N-acylaminopropyl-N, N-dimethylammonium glycinate, coconut oil acylaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazoline, and coconut oil acylaminoethyl Hydroxyethyl carboxymethyl glycinate, N-alkylbetaine, N-alkylaminobetaine. Examples of suitable mild surfactants as dispersants are surfactants that are particularly well tolerated by the skin, such as aliphatic alcohol polyglycol ether sulfates, monoglyceride sulfates, mono and / or dialkyl sulfosuccinates , Fatty acid isethionate, fatty acid sarcosine, fatty acid tauride, fatty acid glutamate, α-olefin sulfonate, ether carboxylic acid, alkyl oligoglucoside, fatty acid glucamide, alkylamide betaine, and / or preferably protein based on wheat protein It is a fatty acid condensate. Nonionic surfactants such as PEG-6 beeswax (and) PEG-6 stearate (and) polyglyceryl-2 [Apifac] isostearate, glyceryl stearate (and) PEG-100 stearate [Arlacel 165], stearic acid PEG-5 glyceryl (arlatone 983 S), sorbitan oleate (and) polyglyceryl-3 ricinoleate [Arlacel 1689], sorbitan stearate and palm fatty acid sucrose [arlatone 2121], glyceryl stearate and laureth-23 [Cerasynth 945], Cetearyl alcohol and ceteth-20 [Cetomacrogol Wax], cetearyl alcohol and polysorbate 60 and PEG-150 and stearate -20 [Polawax GP 200, Polawax NF], cetearyl alcohol and cetearyl polyglucoside [Emulgade PL 1618], Cetearyl alcohol and ceteares-20 [Emulgade 1000NI, Cosmowax], cetearyl alcohol and PEG-40 castor oil [Emulgade F Specia l], cetearyl alcohol and PEG-40 castor oil and sodium cetearyl sulfate [Emulgade F], stearyl alcohol and steareth-7 and steareth-10 [Emulgator E 2155], cetearyl alcohol and steareth-7 and steareth-10 [Emulsifying wax USNF], glyceryl stearate and PEG-75 stearate [Gelot 64], propylene glycol ceteth-3 [Hetester PCS], propylene glycol-8-isoses-3 [Hetester PHA], cetearyl alcohol and ceteth-12 And Ores-12 [Lanbritol Wax N21], PEG-6 stearate and PEG-32 stearate [Tefose 1500], PEG-6 and ceteth-20 and ceteares-20 [Tefose 2000], PEG-6 stearate and Ceteth-20 and glyceryl stearate and steareth-20 [Tefose 2561], glyceryl stearate and ceteares-20 [Teginacid H, C, X]. Anionic emulsifiers such as PEG-2 SE stearate, glyceryl stearate SE [Monelgine, Cutina KD], propylene glycol stearate [Tegin P], cetearyl alcohol and cetearyl sulfate [Lanette N, Cutina LE, Crodacol GP], Cetearyl alcohol and sodium lauryl sulfate [Lanette W], trilanes-4 phosphate and glycol stearate and PEG-2 stearate [Sedefos 75], glyceryl stearate and sodium lauryl sulfate [Teginacid Special]. Cationic acid bases such as cetearyl alcohol and cetrimonium bromide. The most preferred dispersant (b) is a sodium alkyl sulfate or sodium alkyl ether sulfate such as sodium laureth sulfate [Texapon N70 from Cognis] or sodium milles sulfate [Texapon K14S from Cognis]. Certain dispersants may be used in amounts of, for example, 1-30% by weight, in particular 2-20% by weight and preferably 3-10% by weight, based on the total weight of the composition. Useful solvents are water, saturated saline, (poly) ethylene glycol, glycerol or cosmetically acceptable oils. Other useful solvents are entitled “Esters of fatty acids”, “natural and synthetic triglycerides, including glyceryl esters and derivatives”, “pearly waxes”, “hydrocarbon oils” and “silicones or siloxanes” below. It is disclosed in the item.

  Where the formulation according to the invention corresponds to water and oil-containing emulsions (e.g. W / O, O / W, O / W / O and W / O / W emulsions or microemulsions), e.g. the total weight of the composition UV filter selected from 0.1 to 30% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 10% by weight, (a)-(x), 1 to 60 relative to the total weight of the composition % By weight, in particular 5-50% by weight, preferably 10-35% by weight of at least one oil component, 0-30% by weight, in particular 1-30% by weight, preferably 4%, based on the total weight of the composition -20% by weight of at least one emulsifier, 10-90% by weight, in particular 30-90% by weight of water, 0-88.9% by weight, in particular 1-50% by weight of further cosmetics, based on the total weight of the composition As an acceptable adjuvant.

Suitable oil components of oil-containing compositions (e.g. oils, W / O, O / W, O / W / O and W / O / W emulsions or microemulsions) are for example 6-18, preferably 8-10. Gerve alcohols based on aliphatic alcohols having one carbon atom, esters of linear C ₆ -C ₂₄ fatty acids with linear C ₃ -C ₂₄ alcohols, branched C ₆ -C ₁₃ carboxylic acids and linear Esters of C ₆ -C ₂₄ aliphatic alcohols, linear C ₆ -C ₂₄ fatty acids and branched alcohols, especially esters of 2-ethylhexanol, hydroxycarboxylic acids and linear or branched C ₆ -C ₂₂ fatty alcohols, in particular esters of dioctyl malate, linear and / or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer diol or trimer triol) and / or Guerbet alcohols esters of, birds based on C ₆ -C ₁₀ fatty acids Riserido, C ₆ -C ₁₈ liquid mono- / di- / triglyceride mixtures based on fatty acids, C ₆ -C ₂₄ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular esters of benzoic acid, C ₂ -C ₁₂ dicarboxylic Esters of acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxy groups, vegetable oils (e.g. sunflower oil, olive oil) , Soybean oil, rapeseed oil, almond oil, jojoba oil, orange oil, malt oil, peach seed oil and coconut oil liquid component), branched primary alcohol, substituted cyclohexane, linear and branched C ₆ ~ C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ alcohols (e.g., Finsolv (R) TN), total of 12 to 36 Pieces of carbon Linear or branched, symmetrical or asymmetrical dialkyl ethers having atoms, in particular 12 to 24 carbon atoms, such as di-n-octyl ether, di-n-decyl ether, di-n-nonyl ether, Di-n-undecyl ether, di-n-dodecyl ether, n-hexyl n-octyl ether, n-octyl n-decyl ether, n-decyl n-undecyl ether, n-undecyl n-dodecyl ether, n- Hexyl n-undecyl ether, di-tert-butyl ether, diisopentyl ether, di-3-ethyl decyl ether, tert-butyl n-octyl ether, isopentyl n-octyl ether and 2-methylpentyl-n-octyl ether; Ring-opening products of epoxidized fatty acid esters and polyols, silicone oils and / or aliphatic or naphthenic hydrocarbons. Also important are monoesters of fatty acids and alcohols having 3 to 24 carbon atoms. This group of substances includes fatty acids having 8 to 24 carbon atoms such as caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid. , Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, behenic acid and erucic acid and mixtures of these technical grades (e.g. pressurization of natural fats and oils) Under removal, under the reduction of aldehydes from the oxo synthesis of rhylene or in dimerization of unsaturated fatty acids) and alcohols such as isopropyl alcohol, capron alcohol, capryl alcohol, 2-ethylhexyl alcohol, caprin alcohol, Lauryl alcohol, Sotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petrocerinyl alcohol, linoyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachidyl alcohol , Gadreyl alcohol, behenyl alcohol, erucyl alcohol and brassyl alcohol and mixtures of these technical grades (e.g. in the high-pressure hydrogenation of aldehydes from oxo synthesis of technical grade methyl esters or rhylenes based on oils and unsaturated fats) Product obtained as a monomer fraction in the dimerization of aromatic alcohols). Of particular interest, isopropyl myristate, isononanoic acid C ₁₆ -C ₁₈ alkyl esters, stearic acid 2-ethylhexyl ester, cetyl oleate, capric acid glycerol, coconut fatty alcohols caprinate / caprylate and stearic acid n- Butyl. Further oil components that can be used are dicarboxylic acid esters such as di-n-butyl adipate, di (2-ethylhexyl) adipate, di (2-ethylhexyl) succinate and diisotridecyl acetate, and diol esters such as ethylene. Glycol dioleate, ethylene glycol diisotridecanoate, propylene glycol di (2-ethylhexanoate), propylene glycol diisostearate, propylene glycol dipelargonate, butanediol diisostearate and neopentyl glycol dicapri Rate. Preferred mono or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol. It is also possible to use divalent and / or trivalent metal salts of one or more alkyl carboxylic acids (alkaline earth metals, especially Al ³⁺ ).

  The oil component can be used, for example, in an amount of 1 to 60% by weight, in particular 5 to 50% by weight, preferably 10 to 35% by weight, based on the total weight of the composition.

  Any conventionally useful emulsifier can be used in the cosmetic composition according to the present invention.

Suitable emulsifiers are, for example, nonionic surfactants from the following group:
-2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide and a linear aliphatic alcohol having 8 to 22 carbon atoms, a fatty acid having 12 to 22 carbon atoms, and 8 alkyl groups Addition products with alkylphenols having ˜15 carbon atoms, such as cetealess-20 or cetealess-12;
- 1 to 30 mol of ethylene oxide and a polyol having 3 to 6 carbon atoms, in particular C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of glycerol
Glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide adducts, such as glyceryl stearate, glyceryl isostearate, glyceryl oleate, sorbitan oleate, sesquioxide Sorbitan oleate;
- C ₈ -C ₂₂ alkyl - mono and oligo - glycosides and their ethoxylated analogues, degree of oligomerization is 1.1 to 5, especially 1.2 to 1.4 are preferred, glucose is preferred as the sugar component;
-Addition products of 2 to 60 mol, in particular 15 to 60 mol of ethylene oxide with castor oil and / or hydrogenated castor oil;
-Polyol esters, in particular polyglycerol esters, such as diisostearoyl polyglyceryl-3 diisostearate, polyglyceryl-3 diisostearate, triglyceryl diisostearate, polyglyceryl-2 sesquiisostearate or polyglyceryl dimerate. Mixtures of compounds from several of these substance classes are also suitable;
- linear, branched, unsaturated or saturated C ₆ -C ₂₂ fatty acids, ricinoleic acid and also based on the 12-hydroxystearic acid, and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g., Sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside), and also polyglucosides (e.g. cellulose), e.g. partial esters based on polyglyceryl-2-dihydroxystearate or polyglyceryl-2-diricinoleate;
Mono-, di- and tri-alkyl phosphates and also mono-, di- and / or tri-PEG-alkyl phosphates and their salts;
-Wool wax alcohol
-One or more ethoxylated esters of natural derivatives, for example polyethoxylated esters of hydrogenated castor oil;
-Silicone oil emulsifiers, e.g. silicone polyols;
-Polysiloxane / polyalkyl / polyether copolymers and corresponding derivatives, such as cetyl dimethicone copolyol;
-Mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohols (see DE-A-1 165574) and / or fatty acids having 6 to 22 carbon atoms, methyl glucose and polyols, preferably glycerol or polyglycerol, For example polyglyceryl-3-glucose distearate, polyglyceryl-3-glucose dioleate, methyl glucose dioleate or dicocoylpentaerythrityl distearyl citrate; and also
-Polyalkylene glycol.

Addition products of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and di-esters and also sorbitan mono- and di-esters of fatty acids or with castor oil are known commercial products It is. These are usually homologous mixtures whose average degree of alkoxylation corresponds to the ratio of the amount of ethylene oxide and / or propylene oxide to the amount of substrate on which the addition reaction is carried out. C ₁₂ -C ₁₈ fatty acid mono- and di-esters of addition products of ethylene oxide and glycerol are known, for example, from DE-A-2024051 as fat recovery substances for cosmetic preparations.

C ₈ -C ₁₈ alkyl-mono and oligo-glycosides, their preparation and their use are known from the prior art. These are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. Suitable glycoside groups include monoglycosides in which a cyclic sugar group is glycoside bonded to an aliphatic alcohol, and preferably oligomeric glycosides having an oligomer degree of up to about 8. The degree of oligomer is a statistical average based on the usual homolog distribution for such technical grade products.

It is also possible to use zwitterionic surfactants as emulsifiers. The term “zwitterionic surfactant” refers in particular to a surface-active compound having at least one quaternary ammonium group and at least one carboxylate and / or sulfonate group in the molecule. Particularly suitable zwitterionic surfactants are so-called betaines such as N-alkyl-N, N-dimethylammonium glycinate, such as cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethyl-ammonium. Glycinates such as cocoasilaminopropyldimethylammonium glycinate and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazoline (in each case having 8 to 18 carbon atoms in the alkyl or acyl group) and also Cocoasil aminoethyl hydroxyethyl carboxymethyl glycinate. Particularly preferred are the known fatty acid amide derivatives under the CTFA name cocamidopropyl betaine. Likewise suitable as emulsifiers are amphoteric surfactants. Amphoteric surfactants in particular contain at least one free amino group and at least one —COOH or —SO ₃ H group in the molecule in addition to containing a C ₈ -C ₁₈ alkyl or acyl group, It is understood to mean something that can form an internal salt. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyl Includes taurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid (in each case having about 8-18 carbon atoms in the alkyl group).

Particularly preferred amphoteric surfactants are N-cocoalkylamino-propionate, cocoacylaminoethylaminopropionate and C ₁₂ -C ₁₈ acyl sarcosine. In addition to amphoteric emulsifiers, quaternary emulsifiers are also considered, particularly preferred are those of the ester quaternary type, preferably methyl-quaternized divalent fatty acid triethanolamine ester salts.

  Nonionic emulsifiers, preferably ethoxylated fatty alcohols having 8 to 22 carbon atoms and 4 to 30 EO units are preferred.

  The emulsifier may be used, for example, in an amount of 1 to 30% by weight, in particular 4 to 20% by weight and preferably 5 to 10% by weight, based on the total weight of the composition. However, it is also possible in principle to disperse using emulsifiers.

  The compositions according to the invention, such as creams, gels, lotions, alcohols and aqueous / alcohol solutions, emulsions, wax / fat compositions, stick formulations, powders or ointments are further used as mild adjuvants as further adjuvants and additives , Super fat, pearlescent wax, consistency regulator, thickener, polymer, silicone compound, fat, wax, stabilizer, biologically active ingredient, deodorant active ingredient, anti-dandruff agent, A film-forming agent, swelling agent, antioxidant, hydrotrope agent, preservative, insect repellent, self-tanning agent, solubilizer, perfume oil, colorant, bacteria inhibitor and the like may be contained.

  Substances suitable for use as overfat agents are, for example, lanolin and lecithin, and also polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter also acting as foam stabilizers at the same time. To do.

  Examples of suitable mild surfactants, i.e. surfactants that exhibit particularly good resistance to the skin, are aliphatic alcohol polyglycol ether sulfates, monoglyceride sulfates, mono and / or di-alkyl sulfosuccinates, fatty acid isethions Salt, fatty acid sarcosine, fatty acid tauride, fatty acid glutamate, α-olefin sulfonate, ether carboxylic acid, alkyl oligoglucoside, fatty acid glucamide, alkylamide betaine, and / or protein fatty acid condensate, the latter being preferred Is based on wheat protein.

  Suitable nacres are for example: alkylene glycol esters, especially ethylene glycol distearate; fatty acid alkanolamides, especially coconut oil fatty acid diethanolamine; partial glycerides, especially stearic acid monoglycerides; polyvalent, unsaturated or hydroxy-substituted carboxylic acids and 6-22. Esters with aliphatic alcohols having 1 carbon atom, in particular long-chain esters of tartaric acid; fatty substances such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and aliphatic carbonates (generally at least 24 carbon atoms Laurones and distearyl ethers; fatty acids such as stearic acid, hydroxystearic acid or behenic acid, olefin epoxides having 12 to 22 carbon atoms and aliphatic alcohols having 12 to 22 carbon atoms Ring-opening products and / or Or polyols having 2 to 15 carbon atoms and 2 to 20 hydroxyl groups, and mixtures thereof.

  Suitable consistency regulators are in particular aliphatic alcohols or hydroxy aliphatic alcohols having 12 to 22 carbon atoms, preferably 16 to 18 carbon atoms, and also partial glycerides, fatty acids and hydroxy fatty acids. Combinations of these substances with alkyl-oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearate are preferred. Suitable thickeners are, for example, Aerosil type (hydrophilic silicic acid), polysaccharides, in particular xanthan gum, guar gum, agar, alginate and tyrose, carboxymethylcellulose and hydroxyethylcellulose, and relatively high molecular weight fatty acid polyethylene glycol mono- and di- -Surfactants such as esters, polyacrylates (e.g. Carbopol (R) from Goodrich, or Synthalen (R) from Sigma), polyacrylamide, polyvinyl alcohol and polyvinyl pyrrolidone, ethoxylated fatty acid glycerides, pentaerythritol or tri Contains esters of fatty acids with polyols such as methylolpropane, fatty alcohol ethoxylates with a limited homolog distribution and alkyl-oligoglucosides and electrolytes such as sodium chloride or ammonium chloride. .

  Suitable cationic polymers are, for example, cationic cellulose derivatives such as copolymers of quaternized hydroxymethylcellulose, cationic starch, diallylammonium salt and acrylamide, available under the name Polymer JR 400® from Amerchol. Quaternized vinylpyrrolidone / vinylimidazole polymers such as Luviquat® (BASF), polyglycol and amine condensation products, quaternized collagen polypeptides such as lauryl dimonium hydroxypropyl hydrolyzed collagen (Lamequat® L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as amide methicone or adipic acid and dimethylaminohydroxypropyldiethylenetriamine (Cartaretin® / Sandoz) Copolymers of lauric acid and dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), such as the polyaminopolyamides described in FR-A-2 252840, and their crosslinked water-soluble polymers, cationic chitin derivatives such as Quaternized chitosan, optionally distributed as microcrystalline, dihaloalkyl, for example condensates of dibromobutane with bisdialkylamines, for example bisdimethylamino-1,3-propane, cationic guar gum, for example from Celanese Jaguar® C-17, Jaguar® C-16, quaternized ammonium salt polymers such as Mirapol® A-15, Mirapol® AD-1, Mirapol (Miranol) (Registered trademark) AZ-1.

  Suitable anionic, zwitterionic, amphoteric and nonionic polymers are for example vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers, vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / Maleic anhydride copolymer and its esters, uncrosslinked polyacrylic acid and polyacrylic acid crosslinked with polyol, acrylamidopropyltrimethylammonium chloride / acrylate copolymer, octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate Copolymer, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone / dimethylaminoethyl methacrylate / vinyl caprolactam ter Polymers, and also optionally derivatized cellulose ethers and silicones.

  Suitable silicone compounds are, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic silicones, which may be either in liquid or resin form at room temperature, and also amino-, fatty acid-, alcohol-, polyether-, epoxy -, Fluorine-, glycoside- and / or alkyl-modified silicone compounds. Another suitable is simethicone, which is a mixture of dimethicone and hydrogenated silicate having an average chain length of 200 to 300 dimethylsiloxane units. A detailed investigation by Todd et al. On suitable volatile silicones can be found further in Cosm. Toil. 91, 27 (1976).

  Typical examples of fats are glycerides, taking into account waxes, among others beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax, hard castor oil and fatty acid esters or optionally hydrophilic waxes such as cetylstearyl alcohol or partial glycerides. It is a microwax that is solid at room temperature in combination. Metal salts of fatty acids such as stearic acid or magnesium ricinoleate, aluminum and / or zinc may be used as stabilizers.

  Biologically active ingredients include, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acid, amino acid, ceramide, pseudoceramide, essential oil, plant It should be understood as meaning extract and vitamin complex.

Suitable deodorant active ingredients are, for example, antiperspirants such as aluminum chlorohydrate (see J. Soc. Cosm. Chem. 24, 281 (1973)). Particularly preferred is the aluminum chlorohydrate corresponding to the formula Al ₂ (OH) ₅ Clx2.5H ₂ O known as Hoechst AG, the trademark Locron® of Frankfurt (FRG) (J. Pharm. Pharmacol 26, 531 (1975)). In addition to chlorohydrate, it is also possible to use aluminum hydroxy-acetate and acidic aluminum / zirconium salts. An esterase inhibitor may be added as a further deodorant active ingredient. Such inhibitors are preferably trialkyl citrates such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, and in particular triethyl citrate (Hydagen® CAT, Henkel KGaA, Düsseldorf / FRG), which inhibit enzyme activity and thus reduce odor formation. Further suitable esterase inhibitors are sterol sulfates or phosphates such as lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfates or phosphates, dicarboxylic acids and esters thereof such as glutaric acid, glutaric acid monoethyl ester, glutaric acid Diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester and hydroxycarboxylic acid and its esters such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester. Antimicrobial active ingredients that affect the flora, kill sweat-degrading bacteria or inhibit their growth can likewise be present in the formulation (especially stick formulations). Examples include chitosan, phenoxyethanol and chlorhexidine gluconate. 5-Chloro-2- (2,4-dichlorophenoxy) -phenol (Irgasan®, BASF) has also proven to be particularly effective.

  Conventional film formers include, for example, chitosan, microcrystalline chitosan, quaternized chitosan, polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, polymers of quaternary cellulose derivatives containing a high proportion of acrylic acid, collagen , Hyaluronic acid and its salts, and similar compounds. Suitable swelling agents for the aqueous phase are montmorillonite, clay minerals, Pemulen, and also the alkyl modified type Carbopol (Goodrich). Further suitable polymers and swelling agents can be found in the review of Cosm. Toil. 108, 95 (1993) by R. Lochhead.

  It is also possible to use hydrotropic agents such as ethanol, isopropyl alcohol or polyols to improve flowability. Suitable polyols for this purpose preferably contain 2 to 15 carbon atoms, at least 2 hydroxy groups.

The polyol may further contain functional groups, in particular amino groups, and / or may be modified with nitrogen. A typical example is:
-Glycerol;
-Alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and also polyethylene glycols having an average molecular weight of 100 to 1000 daltons;
-Technical oligoglycerol mixtures with a degree of intrinsic condensation of 1.5-10, e.g. industrial diglycerol mixtures with a diglycerol content of 40-50% by weight;
-Methylol compounds, such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
Lower alkyl-glucosides, especially those having 1 to 8 carbon atoms in the alkyl group, such as methyl and butylglucoside;
-Sugar alcohols having 5 to 12 carbon atoms, such as sorbitol or mannitol;
-Sugars having 5 to 12 carbon atoms, such as glucose or saccharose;
-Amino sugars such as glucamine;
Dialcoholamines, such as diethanolamine or 2-amino-1,3-propanediol.

  Suitable preservatives include, for example, phenoxyethanol, formaldehyde solutions, parabens, pentanediol or sorbic acid, and also the substance classifications listed in Schedule 6, Parts A and B of the Cosmetics Regulations.

  Suitable perfume oils are mixtures of natural and / or synthetic fragrances. Representative of natural fragrances are, for example, from flowers (lily, lavender, rose, jasmine, neroli, ylang ylang), stems and leaves (geranium, patchuri, petitgren), fruits (anise seeds, coriander, fennel, mice). , Fruit peel (bergamot, lemon, orange), roots (mace, angelica, celery, cardamom, costas, iris, shabu), trees (pine tree, sandalwood, guayak tree, cedar tree, rosewood) From herbs and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, pine, red pine, red pine), resin and balsam (galvanum, elemi, benzoin, myrrh, frankincense, opopanax) Is an extract from Animal materials such as civet and castrium are also taken into account. Typical synthetic fragrances are for example products of esters, ethers, aldehydes, ketones, alcohols or hydrocarbons.

  Aromatic compounds of esters include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl glycinate Methyl phenyl, allyl cyclohexyl propionate, styryl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether; aldehydes include, for example, linear alkanals having 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lyial. Ketones include, for example, ionones, α-isomethylionone and methyl cedryl ketone; alcohols include, for example, anethole, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and Contains terpinol; and carbohydrates mainly include terpenes and balsams. However, it is preferred to use a mixture of various aromatic substances that together produce an attractive scent. Used mainly as an aromatic component, relatively low volatility ether oils such as sage oil, chamomile oil, clove oil, melissa oil, cinnamon leaf oil, lime flower oil, mud seed oil, vetiver oil, Milk perfume oil, galvanum oil, labranum oil and lavandin oil are also suitable as perfume oils. Bergamot oil, dihydromyrsenol, lyial, rilal, citronellol, phenylethyl alcohol, α-hexylcinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, voice ambrenforte, ambroxan, indole, hedione, sandelis, lemon oil , Tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, β-damascone, bourbon geranium oil, cyclohexyl salicylate, bart fix school, iso-E-super, Fixolide NP, evanil, illardine It is preferable to use gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, lomira, irotyl and flora, alone or mixed with each other.

  Suitable colorants recognized for cosmetic purposes are disclosed, for example, in Farbstoffkommission der Deutschen Forschungsgemeinschaft “Kosmetische Farbemittel”, Verlag Chemie, Weinheim, 1984, pages 81-106. Colorants are generally used at a concentration of 0.001 to 0.1% by weight, based on the total mixture.

  Typical examples of bacterial inhibitors are 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di (4-chlorophenyl-biguanide) hexane) or TCC (3,4,4'-trichloro It is a preservative having a specific action against Gram-positive bacteria such as carbanilide).

  Many aromatic substances and ether oils also have antibacterial properties. Typical examples are the eugenol, menthol and thymol active ingredients in clove oil, mint oil and thyme oil. The natural deodorant of interest is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-todecatrien-1-ol) present in lime flower oil. Glycerol monolaurate has also been proven to be a bacteriostatic agent. The amount of additional bacterial suppressor present is usually 0.1-2% by weight, based on the solids content of the cosmetic composition according to the invention.

The cosmetic composition according to the present invention further comprises an antifoaming agent such as silicone, a structural material such as maleic acid, a solubilizing agent such as ethylene glycol, propylene glycol, glycerol or diethylene glycol, latex, styrene / PVP or styrene / Milky agents such as acrylamide copolymers, complexing agents such as EDTA, NTA, β-alanine diacetic acid or phosphonic acid, propane / butane mixtures, propellants such as N ₂ O, dimethyl ether, CO ₂ , N ₂ or air, oxidation dyes So-called coupler and developer components such as precursors, thioglycolic acid and its derivatives, reducing agents such as thiolactic acid, cysteamine, thiomalic acid or α-mercaptoethanesulfonic acid, or hydrogen peroxide, potassium bromide or sodium bromide An oxidizing agent such as

  Insect repellents are, for example, N, N-diethyl-m-toluamide, 1,2-pentanediol or insect repellent 3535.

  Suitable self-tanning agents are dihydroxyacetone, erythrulose or a mixture of dihydroxyacetone and erythrulose.

The cosmetic preparations according to the invention are contained in various cosmetic preparations, in particular the following preparations:
-Skin care preparations, e.g. skin emulsions, multi-emulsions or skin oils;
-Cosmetic personal care preparations such as facial makeup in the form of day cream or powder cream, funny (powder or solid), blusher or cream makeup, eye care preparations such as eye shadow preparations, mascara, eyeliner, eye Cream or eye fix cream; lip care preparations such as lipsticks, lip glosses, lip contour pencils; nail care preparations such as nail lacquers, nail lacquer removers, nail hardeners or cuticle removers;
-Light protection preparations such as sun milk, lotion, cream or oil, sun block or tropical, pretanning preparation or after sun preparation;
-Skin tanning preparations, e.g. self-tanning creams;
-Bleaching preparations, e.g. preparations for bleaching the skin, or whitening preparations;
-Insect repellents, such as insect repellent oils, lotions, sprays or sticks;

The final formulation can be in various forms, for example:
-In the form of liquid preparations such as W / O, O / W, O / W / O, W / O / W or PIT emulsions and all types of microemulsions,
-In the form of a gel,
-In the form of oil, cream, milk or lotion,
-In the form of powder, lacquer, tablets or make-up,
-In the form of a stick,
-In the form of spray (spray containing propellant gas or pump spray) or aerosol,
-In the form of bubbles, or
-May exist in the form of a paste.

  Cosmetic compositions important for the skin are sun milk, lotions, creams, oils, sunblocks or tropicals, pretanning preparations or aftersun preparations, and light protection such as skin tanning preparations, for example self-tanning creams It is a preparation. Of particular interest are sun protection creams, sun protection lotions, sun protection oils, sun protection milks and sun protection preparations in spray form.

A. Examples of UV Filters and UV Filter Combinations According to the Invention Calculation of Sunscreen Spectral Transmittance T (λ) For the calculation of sunscreen spectral transmittance T (λ) for a given filter composition, a simulation tool can be used. used. The tool is based on the following factors: database of UV spectra of relevant UV filters (shown as decade molar extinction coefficient), mathematical description of irregular profile of sunscreen film on the skin, UV due to light instability Examination of changes in filter concentration and the effect of formulation such as UV filter distribution in the oil and water phases of the emulsion.

Determination of the decay rate AF _vd of SPF (erythema attenuation) and previtamin D formation
1 MED (minimal erythema dose, which is a is a minimum amount of UV-B radiation after 24 hour exposure) systemic exposure to erythema radiation exposure = 250 J / m ² erythema radiation exposure is, of vitamin D ₃ of about 10,000IU oral Corresponding to ingestion is known from the scientific literature. With maximum solar input (according to COLIPA, mid-day sun, good weather), it takes about 20 minutes to receive 1MED. Recommended intake of vitamin D ₃ ranges from 1,000 to 4,000 IU per day. A daily supply of 2000 IU per day is recommended by DGE (Deutsche Gesellschaft fur Ernahrung 2011). This recommendation, for example by not exposed to UV radiation, to the lack of endogenous / epidermal vitamin D ₃ production. Under conditions where unprotected skin is exposed to the maximum solar input, after f 20/5 = 4 minutes, this amount of vitamin D ₃ can be produced in the skin. Sunscreen attenuates erythema irradiation and vitamin D ₃ -effective radiation.

MED = minimum erythema dose = minimum amount of UVB radiation [J / m ² ] = 250 J / m ² that produces the first redness in the skin 24 hours after exposure (reference value) 1 IU = 25 ng vitamin D ₃ .

SPF is calculated by the following formula

E_λ(λ) 分光日射照度(spectral solar irradiance)
T(λ) 所与の日焼け止めの分光透過率
S_er(λ) 紅斑の作用スペクトル
S_pvd(λ) 皮膚でのビタミンD₃形成の作用スペクトル Similar to SPF, the decay rate of vitamin D _{3 -effective} radiation AF _PVD is defined as:

E _λ (λ) Spectral solar irradiance
T (λ) Spectral transmittance of a given sunscreen
S _er (λ) Erythema action spectrum
S _pvd (λ) Action spectrum of vitamin D ₃ formation in the skin

BASF Sunscreen Simulator: www.basf.com/sunscreensimulator; Herzog, B .; Osterwalder, U. In Silico Determination of Topical Sun Protection. Cosm Sci Tech. 2011; 62: 1-8 E _er , E _VD , E _VD / E _er , SPF, AF _VD calculation

When protected skin is exposed to the maximum solar input mentioned above, the exposure time t _PVD to produce 2,000 IU equivalent to the recommended vitamin D ₃ intake, with or without sunscreen, is
t _PVD = 4 x AF _PVD minutes.

The decay rate AF _PVD and exposure time t _PVD for some examples of sunscreens are shown in Table 4.

  Examples of filter compositions are selected to achieve sun protection factors (abbreviated SPF) 6, 15, and 30.

result
[Example A1]
SPF6 Sunscreens Table 1 shows the compositions for the above four SPF6 sunscreens and the calculated values of SPF, E _pvd / E _er ratio, UVA-PF, UVA-PF / SPF ratio and critical wavelength CW.

  FIG. 3 shows the spectral transmission of sunscreen films for four different types of UV filter compositions resulting in SPF6.

[Example A2]
SPF15 Sunscreens Table 2 shows the compositions for the four SPF15 sunscreens and calculated values for SPF, E _pvd / E _er ratio, UVA-PF, UVA-PF / SPF ratio, and critical wavelength CW.

  In FIG. 4, the simulated spectral transmission of sunscreen films for four different types of UV filter compositions that provide SPF15 is shown.

[Example A3]
SPF30 Sunscreens Table 3 shows the compositions for the four SPF30 sunscreens and calculated values for SPF, E _pvd / E _er ratio, UVA-PF, UVA-PF / SPF ratio, and critical wavelength CW.

  FIG. 5 shows the simulated spectral transmission of sunscreen films for four different types of UV filter compositions that yield SPF30.

Examples A3.3 and A3.4 demonstrate that the transmittance of sunscreen for vitamin D ₃ -effective radiation can be optimized even when the SPF is the same.

[Example A4]
Determining the recommended amount of vitamin D per day
The exposure time t _PVD to obtain a recommended vitamin D intake of 2000 IU per day is t _PVD = 4 × AF _PVD minutes if the protected skin is exposed to the maximum solar input mentioned above. The decay rate AF _PVD and exposure time t _PVD for the four sunscreen examples are shown in Table 4.

For example, the exposure time t _PVD for sun exposure using a sunscreen with SPF = 30 is about 2 hours, which is within the normal time frame for sunbathing. Therefore, optimizing sunscreen is actually meaningful in terms of decreasing the decay rate AF _PVD .

B. Examples for cosmetic preparations

  The formulation is prepared as follows: Part A and B are prepared and heated separately to 80 ° C. Part A is then added to Part B with stirring. After brief homogenization, add Part C with stirring. After cooling to room temperature, the Part D ingredients are added in the order listed.

  The formulation is prepared as follows: Part A is heated to 80 ° C., cooled to room temperature, and charged to Part B with stirring. After homogenization (using an ultra-turrax type device), part C is added and then homogenized again. Finally, the Part D ingredients are added and the formulation is homogenized again.

  The formulation is prepared as follows: Part A and B are prepared and heated separately to 80 ° C. Part A is then added to Part B with stirring. After brief homogenization, add Part C with stirring. After cooling to room temperature, the Part D ingredients are added in the order listed.

  The formulation is prepared as follows: Part A and B are prepared and heated separately to 80 ° C. Part A is then added to Part B with stirring. After brief homogenization, add Part C with stirring. After cooling to room temperature, the Part D ingredients are added in the order listed.

  The formulation is prepared as follows: Part A and B are prepared and heated separately to 80 ° C. Part A is then added to Part B with stirring. After brief homogenization, add Part C with stirring. After cooling to room temperature, the Part D ingredients are added in the order listed.

The formulation is prepared as follows: Part A and B are prepared and heated separately to 80 ° C. Part A is then added to Part B with stirring. After brief homogenization, add Part C with stirring. After cooling to room temperature, the Part D ingredients are added in the order listed.

Claims (18)

(a) a triazine derivative;
(b) cinnamic acid derivatives;
(c) bis-resorcinyl triazine;
(f) benzimidazole derivatives;
(i ₅₎ 4-methyl benzylidene camphor;
(h) a benzoylpiperazine derivative;
(j) benzoxazole derivatives;
(k) a diarylbutadiene derivative;
(l) phenylbenzotriazole derivatives;
(n) benzylidene malonate;
(o ₃ ) salicylic acid TEA;
(r) an imidazoline derivative;
(u) an inorganic UV filter selected from metal oxides;
(v) naphthalate; and
(w) comprising at least one UV filter (A) selected from merocyanine derivatives; and optionally
(d) an aminobenzophenone derivative;
(e) a dibenzoylmethane derivative;
(g) β, β-diphenyl acrylate derivative;
(i ₅ ) different camphor derivatives;
(o ₃ ) different salicylate derivatives;
(p) an anthranilate derivative; and
(s) a sunscreen formulation comprising at least one UV filter (B) selected from benzalmalonate derivatives,
-To increase the transmission of UV radiation in human skin for the production of cholecalciferol (pre-vitamin D ₃ ), and at the same time, make human skin against UV radiation when exposed to sunlight A method for protecting, for use in a method comprising applying the sunscreen formulation to the skin,
A sunscreen preparation wherein the ratio R of the effective dose E _{pvd for previtamin} D ₃ formation to the effective dose E _er for erythema formation in the skin is at least 1.8.   A sunscreen formulation according to claim 1 having at least two SPFs.   The sunscreen formulation according to claim 1, having at least 6 SPFs. UV filter
(a ₁ ) ethylhexyltriazone;
(a ₂ ) tris-bephenyltriazine;
(a ₃ ) diethylhexylbutamide triazone;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(g ₁ ) octocrylene;
(h ₁ ) 1,4- (2- (4-diethylamino-2-hydroxybenzoyl) benzoyl) piperazine;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(l ₆ ) 2- (2H-benzotriazol-2-yl) -6- (2-ethylhexyloxymethyl) -4-methyl-phenol;
(i ₁ ) terephthalylidene dicamphor sulfonic acid;
(n ₁ ) a compound of formula (BM9);
(o ₁ ) ethylhexyl salicylate;
(o ₄ ) homosalate;
(p ₁ ) menthyl anthranilate;
(s ₁ ) Polysilicone-15;
(u ₁ ) zinc oxide; and
The sunscreen preparation according to any one of claims 1 to 3, selected from (u ₃ ) titanium dioxide. UV filter
(a ₁ ) ethylhexyltriazone;
(b ₁ ) ethylhexyl methoxycinnamate;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid;
(g ₁ ) octocrylene; and
The sunscreen preparation according to any one of claims 1 to 4, selected from (u ₃ ) titanium dioxide. UV filter
(b ₁ ) ethylhexyl methoxycinnamate;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid; and
(g ₁ ) octocrylene;
The sunscreen preparation according to any one of claims 1 to 5, which is selected from: UV filter
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol; and
The sunscreen preparation according to any one of claims 1 to 6, selected from (e ₁ ) butylmethoxydibenzoylmethane.   The sunscreen formulation according to any one of claims 5 to 7, having at least 6 SPFs. UV filter
(a) 0.1-40% bw triazine derivative;
(b) 0.1-30% bw cinnamic acid derivative;
(c) 0.1-10% bw bis-resorcinyl triazine;
(f) 0.1-10% bw benzimidazole derivative;
(i ₅ ) 0.1-10% bw 4-methylbenzylidene camphor;
(h) 0.1-10% bw benzoylpiperazine derivative;
(j) 0.1-10% bw benzoxazole derivative;
(k) 0.1-20% bw diarylbutadiene derivative;
(l) 0.1-30% bw phenylbenzotriazole derivative;
(n) 0.1-20% bw benzylidene malonate;
(o ₃ ) 0.1-15% bw salicylic acid TEA;
(r) 0.1-10% bw imidazoline derivative;
(u) Inorganic UV filter selected from 0.1-50% bw metal oxide;
(v) 0.1-20% bw naphthalate; and
(w) 0.1-20% bw merocyanine derivative;
As well as, in some cases,
(d) 0.1-20% bw aminobenzophenone derivative;
(e) 0.1-5% bw dibenzoylmethane derivative;
(g) 0.1-1% bw of β, β-diphenylacrylate derivative;
(i) 0.1-10% bw camphor derivative different from (i ₅ );
(o) 0.1-35% bw salicylate derivative different from (o ₃ );
(p) 0.1-10% bw anthranilate derivative; and
The sunscreen formulation according to any one of claims 1 to 8, comprising (s) at least one UV filter (B) selected from 0.1 to 10% bw benzalmalonate derivatives. Sunscreen
(a ₁ ) 1-3% bw ethylhexyl triazone;
(b ₁ ) 1-3.5% bw ethylhexyl methoxycinnamate;
(c ₁ ) 0.6-10% bw bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) 0.8-10% bw diethylaminohydroxybenzoyl hexyl benzoate;
(e ₁ ) 2-3% bw butylmethoxydibenzoylmethane;
(f ₁ ) 2-3% bw phenylbenzimidazole sulfonic acid;
(g ₁ ) 2.0-2.5% bw octocrylene;
(l ₁ ) 2 to 7.5% bw methylenebis-benzotriazolyltetramethylbutylphenol; and
(u ₃₎ 3.0~3.5% including UV filters selected from titanium dioxide bw, sunscreen formulation according to any one of claims 1 to 9. Sunscreen
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol; and
(e ₁₎ includes a UV filter combination of butyl methoxydibenzoylmethane,
11. Sunscreen formulation according to any one of the preceding claims, wherein the sunscreen has an SPF of> 15. Sunscreen
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol; and
(e ₁₎ includes a UV filter combination of butyl methoxydibenzoylmethane,
11. A sunscreen formulation according to any one of the preceding claims, wherein the sunscreen has an SPF of> 30. UV filter is broadband (340-400nm spectrum) UV filter
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(u ₁ ) zinc oxide; and, in some cases,
(e ₁ ) butylmethoxydibenzoylmethane;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(i ₁ ) terephthalylidene dicamphor sulfonic acid; and
The sunscreen preparation according to any one of claims 1 to 12, selected from (p ₁ ) menthyl anthranilate. (a) a triazine derivative;
(b) cinnamic acid derivatives;
(c) bis-resorcinyl triazine;
(f) benzimidazole derivatives;
(h) a benzoylpiperazine derivative;
(i ₅₎ 4-methyl benzylidene camphor;
(l) phenylbenzotriazole derivatives;
(n) benzylidene malonate;
(o ₃ ) salicylic acid TEA;
(r) an imidazoline derivative;
(u) an inorganic UV filter selected from metal oxides;
(v) naphthalate; and
(w) including a UV filter selected from merocyanine derivatives;
14. Sunscreen formulation according to any one of the preceding claims, containing only one selected UV filter. UV filter is broadband (340-400nm spectrum) UV filter
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(i ₁ ) terephthalylidene dicamphor sulfonic acid; and
(u ₁ ) zinc oxide;
Selected from
15. A sunscreen formulation according to claim 14, wherein only one selected UV filter is contained. UV filter
(a ₂ ) tris-biphenyltriazine;
(c ₂ ) aqueous dispersion of bis-ethylhexyloxyphenol methoxyphenyl triazine / polymethyl methacrylate;
(h ₁ ) 1,4- (2- (4-diethylamino-2-hydroxybenzoyl) benzoyl) piperazine;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(u ₁ ) zinc oxide; and
The sunscreen preparation according to any one of claims 1 to 15, selected from (u ₃ ) particulate UV filters selected from titanium dioxide. UV filter
(a ₁ ) ethylhexyltriazone;
(a ₃ ) diethylhexylbutamide triazone;
(c ₁ ) bis-ethylhexyloxyphenol methoxyphenyl triazine;
(d ₁ ) hexyl diethylaminohydroxybenzoyl benzoate;
(e ₁ ) butylmethoxydibenzoylmethane;
(f ₁ ) phenylbenzimidazole sulfonic acid;
(f ₂ ) disodium phenyldibenzimidazole tetrasulfonate;
(g ₁ ) octocrylene;
(h ₁ ) 1,4- (2- (4-diethylamino-2-hydroxybenzoyl) benzoyl) piperazine;
(l ₁ ) methylenebis-benzotriazolyltetramethylbutylphenol;
(l ₂ ) drometrizole trisiloxane;
(l ₆ ) 2- (2H-benzotriazol-2-yl) -6- (2-ethylhexyloxymethyl) -4-methyl-phenol;
(i ₁ ) terephthalylidene dicamphor sulfonic acid;
(n ₁ ) a compound of formula (BM9);
(o ₁ ) ethylhexyl salicylate;
(o ₄ ) homosalate;
(p ₁ ) menthyl anthranilate; and
(s ₁ ) Polysilicone-15;
A sunscreen formulation according to any one of the preceding claims, selected from non-particulate UV filters selected from. 18. Sunscreen preparation according to any one of the preceding claims, wherein the ratio of the effective dose E _pvd for vitamin D formation to the effective dose E _er for erythema formation in the skin is> 2.0.

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